JPH05165178A - Processing method, stabilizing solution and modifying solution for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve preservable property of a Magenta image without using a compound releasing formaline or formaldehyde harmful to human body by processing with a specific stabilizing solution or a modifying solution. CONSTITUTION:A photographic sensitive material is processed with the stabilizing solution or the modifying solution containing at least one kind of a compound expressed by a formula or the precursor and at least one kind of a secondary amine compound. In the formula, R is a formyl group, an acyl group, a carboxyl group, an ester group, a carbamoyl group, a heterocyclic group or an allyl group. The carboxyl group is also possible to form a salt (for example Na salt, NH4 salt). And each of the acyl group, the ester group, the carbomoyl group, the hetero cyclic group is also possible to have a substituted group and the substituted group is an alkenyl group, alkenyl group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizing solution or adjusting solution used for processing a silver halide color photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material) and a processing method using the same, and particularly formaldehyde. The present invention relates to a stabilizing solution or adjusting solution having a reduced vapor pressure and excellent stabilization of a dye image, and a processing method using the stabilizing solution or the adjusting solution.

[0002]

2. Description of the Related Art Generally, the basic steps of processing a silver halide color photographic light-sensitive material are a color development step and a desilvering step.
In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. In the subsequent desilvering step, the silver generated in the color developing step is oxidized by the action of an oxidizing agent commonly referred to as a bleaching agent, and then dissolved by a complex ion forming agent of silver ions commonly referred to as a fixing agent. It Through this desilvering process, only the dye image is formed on the color light-sensitive material.

Usually, after these steps, washing treatment is carried out to remove unnecessary treatment liquid components. In the case of color paper or reversal color paper, it is general to complete the process above and proceed to the drying process, but in the process of color negative film or color reversal film, a stabilization process is required in addition to this. is there. Formalin (37% aqueous formaldehyde solution) is used in the stabilizing bath in the final step of these processings, and its purpose is to prevent fading of magenta dye due to residual magenta coupler in the light-sensitive material after processing. Is well known. A slight amount of formaldehyde vapor is generated during preparation of such a stabilizing bath containing formaldehyde and during drying of the light-sensitive material to which the stabilizing solution adheres.

It is known that inhalation of formaldehyde is harmful to the human body, and the Japan Society for Occupational Health recommends 0.5 ppm as a work environment allowable concentration of formaldehyde. Therefore, from the viewpoint of improving the working environment, efforts have been made to reduce the formaldehyde concentration in the stabilizing bath and to switch to a formalin substitute.

As a formalin substitute, for example, JP-A-63-244036 describes a hexamethylenetetramine compound. If this compound is used, the formaldehyde vapor pressure will certainly decrease, but the original purpose, the ability of the magenta dye to prevent fading, will be insufficient, and significant fading will occur within a few weeks even at room temperature.

US Pat. Nos. 4,786,583 and 4
N-methylol compounds such as urea, guanidine, and melamine are described in the specification of 859574 and the like. Further, JP-A-61-75354, JP-A-61-42660 and JP-A-6-75354.
2-255948, JP-A-1-295258, 2
1- (dihydroxyaminomethyl) in No. 54261
Benzotriazoles, N- (morpholinomethyl) or N- (piperidinomethyl) heterocyclic thione described in JP-A-1-230043, etc., and bis (alkylamino) methane, bis (anilino) methane in JP-A-2-153350. Has been done.

However, among these compounds, those having a lower formaldehyde vapor pressure than formalin have poor image storability, and those using an amount necessary for improving the image storability are formaldehyde vapors similar to formalin. The pressure is not sufficient to satisfy both the effect of improving image storability and the reduction of formaldehyde vapor pressure.

Further, since it has an effect of improving image storability as much as formalin, there is a drawback that side effects are likely to occur when a molar amount larger than that of formaldehyde is added. Such side effects include generation of stains, deterioration of storage stability of yellow dyes, cyan dyes and other dyes present in the light-sensitive material, and contamination of processed images due to adhesion to the light-sensitive material.

On the other hand, aldehydes having a specific structure and precursors thereof are described in French Patent No. 1,305,14.
3, JP-A-48-47338, JP-A-57-97530.
No. 62-196659, No. 62-19850,
U.S. Pat. Nos. 2,440,954 and 4,778,74
3 and British Patent No. 706,972. However, although these compounds do not release formaldehyde gas into the air, they have poor image storability as compared with formalin and are not suitable for practical use.

In addition, it is possible to use an aliphatic aldehyde having a specific structure and an alkanolamine in combination for the purpose of preventing yellow stain and sulfuration in US Pat. No. 4,786,5.
No. 83, European Patent Publication No. 345,172, it is effective in preventing sulfidation, but the occurrence of yellow stain and the image storability are improved.
It is not at a satisfactory level compared to formalin.

[0011]

Therefore, it has been strongly desired to develop a technique for remarkably improving the image storability of a magenta dye by means of not releasing formaldehyde gas into the air. That is, a first object of the present invention is to provide a processing method which remarkably improves the storability of a magenta image without using a compound releasing formalin or formaldehyde which is harmful to the human body. A second object of the present invention is to provide a processing method in which the generation of yellow stain is suppressed. A third object of the present invention is to provide an excellent processing method which is excellent in image storability and does not cause adverse effects such as turbidity of the processing solution and formation of precipitates. Also,
A fourth object of the present invention is to provide a processing method that is low in cost and excellent in image storability.

[0012]

Means for Solving the Problems As a result of intensive studies by the present inventors, a stabilizing solution or preparation containing at least one compound represented by the following general formula (I) or a precursor thereof and at least one secondary amine compound is prepared. It has been found that the above object can be achieved by processing a silver halide color photographic light-sensitive material with a solution or a stabilizing solution or an adjusting solution containing them. General formula (I)

[0013]

[Chemical 2]

(In the formula, R represents a formyl group, an acyl group, a carboxyl group, an ester group, a carbamoyl group, a heterocyclic group or an aryl group.)

The combined use of the compound represented by the general formula (I) and the secondary amine compound is extremely effective in the present invention as compared with the compound represented by the general formula (I) alone. The stabilizing solution and the adjusting solution of the present invention can be used for the processing of all light-sensitive materials.

The compound of the present invention will be described in more detail below. First, the compound represented by formula (I) of the present invention or its precursor will be described. R is a formyl group,
It represents an acyl group, a carboxyl group, an ester group, a carbamoyl group, a heterocyclic group or an aryl group. The carboxyl group may form a salt (for example, Na salt, NH ₄ salt).

An acyl group, an ester group, a carbamoyl group,
The heterocyclic group and the aryl group may have a substituent,
Examples of these substituents include an alkyl group (eg, methyl, ethyl, n-propyl, butyl, cyclopropyl, hydroxyethyl, methoxymethyl), an alkenyl group (eg, allyl), an aryl group (eg, phenyl, 4 -Tert-butylphenyl), heterocyclic group (for example, 5-pyrazole, 4-pyrazole), halogen atom (for example, chlorine, bromine, fluorine), nitro group, cyano group, sulfo group, carboxyl group, phosphono group, acyl A group (eg, acetyl, benzoyl, propanoyl),
Sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl group (eg, dodecanesulfinyl), acyloxy (eg, acetoxy), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), carbamoyl group ( For example, carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (eg, sulfamoyl, N-ethylsulfamoyl),
Amino group, alkylamino group (eg, methylamino,
Dimethylamino), acylamino groups (eg acetylamide, benzoylamide), sulfonamide groups (eg methanesulfonamide), imide groups (eg succinimide), ureido groups (eg methylureido), sulfamoylamino groups ( For example, N-methylsulfamoylamino), urethane group (eg, methoxycarbonylamino), alkoxy group (eg, methoxy, ethoxy), alkylthio group (eg, methylthio, octylthio), aryloxy group (eg, phenoxy), An arylthio group (eg, phenylthio),
Examples thereof include a heterocyclic thio group (for example, benzothiazolylthio), a heterocyclic oxy group (1-phenyltetrazole-5-oxy), a formyl group, a hydroxy group or a mercapto group.

R is specifically a formyl group, an acyl group (eg acetyl, benzoyl, nicotinoyl), a carboxyl group (eg carboxyl, carboxylate anion), an ester group (eg methoxycarbonyl, 2-hydroxylethyloxycarbonyl, phenoxycarbonyl), A carbamoyl group (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl,
N, N-bis (2-hydroxylethyl) carbamoyl, N-phenyl, N-methylcarbamoyl), a heterocyclic group (oxygen atom, sulfur atom, nitrogen atom, at least one of which is a ring-constituting atom 5 to 7 members) In the cyclic group, the ring may be a saturated ring or an unsaturated ring, for example, 5-
Cenyl, 5-furyl, 5-pyrrolyl, 5-imidazolyl, 5-pyrazolyl, 6-pyridyl, 5-pyridyl, 4
-Pyridyl, 5-piperazyl, 6-purinyl, isoxazolyl, piperazin-2-yl, morpholinyl) or an aryl group (eg phenyl, naphthyl, 4-methylphenyl, 3-chlorophenyl, 3-methoxyphenyl, 2-hydroxyphenyl, 3 -Hydroxyphenyl, 4-hydroxyphenyl, 3,4-dihydroxyphenyl).

On the other hand, the precursor of the compound represented by the general formula (I) in the present invention is a compound which releases the aldehyde compound represented by the general formula (I) of the present invention when dissolved in water. Examples of these precursors include an adduct of a compound represented by the general formula (I) and bisulfite, an acetal of the compound represented by the general formula (I),
Examples include hemiacetal and Schiff bases of the compound represented by the general formula (I).

A preferred precursor for the compound represented by the general formula (I) is represented by the following general formula (II). General formula (II)

[0021]

[Chemical 3]

(In the formula, R represents a group defined by the general formula (I). X and Y may be the same or different and each is -O-, -S-, -N (R ₃ )-,-. SO-or-
Represents SO ₂ −. R ₃ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group,
Represents an acyl group and a sulfonyl group. In R ₁ , X is -O
-, - S- or -N (R ₃₎ - in which case, hydrogen atoms,
Alkyl group, alkenyl group, aryl group, heterocyclic group,
It represents an acyl group or a sulfonyl group, and when X is —SO— or —SO ₂ —, it represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, —OM, or —O 2 ^— . R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group when Y is —O—, —S— or —N (R ₃ ) —, and Y is -SO- or -SO ₂ - when is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, -OM, -O ^- represent. M represents a hydrogen atom, an alkali metal or NH ₄ . At least two groups out of R ₁ , R ₂ , R ₃ and R may combine with each other to form a 5- to 7-membered ring. It may form a -X-R ₁ and -Y-R ₂ jointly with each other = N-R _3.

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group and sulfonyl group in R ₁ , R ₂ and R ₃ may have a substituent, and these substituents include aryl in R. Examples thereof include substituents that the group may have.

[0024] As the X preferably -O- is preferably a hydrogen atom as R _1, -SO ₂ as Y - is preferable, as R ₂ is -O ^-, or -OM are preferred. The compound of the present invention represented by the general formula (I) or the general formula (II)
Preferred as the precursor represented by R is R
Is an aryl group, more preferably a compound represented by the following general formula (Ia) or a general formula (II
-The precursor represented by a).

[0025]

[Chemical 4]

(Wherein X, Y, R ₁ and R ₂ are represented by the general formula (I
Synonymous with each in I). R _a1 , R _a2 , R _a3 ,
R _a4 and R _a5 may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a sulfo group, a carboxyl group, a phosphono group, an acyl group. , Sulfonyl group, sulfinyl group, acyloxy, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, alkylamino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, urethane group, alkoxy group , An alkylthio group, an aryloxy group, an arylthio group, a heterocyclic thio group, a heterocyclic oxy group, a formyl group, a hydroxy group or a mercapto group. Of the R _{a1 to} R _a5, the ortho groups may be bonded to each other to form a 5- to 7-membered ring. Of these, the group that can have a substituent may be substituted with the substituent that the aryl group of R may have. )

Of the compound represented by the general formula (Ia) or the precursor represented by the general formula (II-a), R _{a1 to} R _a5 in which R _a1 and R _a5 are simultaneously hydrogen atoms. More preferably, at least one of R _{a2 to} R _a4 is a group selected from a sulfo group, a carboxyl group, a phosphono group, a formyl group or a hydroxy group, and further preferably R _{a2 to} R _a4 is a sulfo group. A group selected from a group, a carboxy group, a phosphono group, a formyl group, a hydroxyl group or a hydrogen atom.

Of the compounds represented by the general formula (Ia) or their precursors represented by the general formula (II-a), compounds in which at least one of R _{a1 to} R _a5 is a hydroxyl group are antibacterial agents and antiproliferative agents. It is preferable because it also acts as a fungicide.

On the other hand, the more preferable precursor is a compound represented by the general formula (II-a) wherein X is-.
O-, R ₁ is H, Y is -SO ₂ - and and R ₂ is -O ^- compound or -OH, i.e., is a bisulfite adduct of formula (I-a) compounds represented by .. Further, the aldehyde itself represented by the general formula (I) is more preferable than the precursor.

Specific examples of the compound represented by formula (I) or the precursor thereof according to the present invention are shown below, but the present invention is not limited thereto.

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

Many of the compounds represented by the general formula (I) of the present invention or their precursors are commercially available and can be easily obtained. Also METHOD EN DER ORGANISC
HENCHEMIE (Houben-Weyl) 's BAND E3 "ALDE HYDE", Geo
It can be easily synthesized by a method similar to the method described in rg Thieme Verlag, Stuttgart (1983).

The secondary amine compound of the present invention will be described in detail. Among the secondary amine compounds of the present invention, preferred are compounds having an acid dissociation constant pKa (value in water at room temperature (about 25 ° C.)) of 7 or more, more preferably 8 or more. Preferred secondary amines of the present invention can be represented by the following general formula (III). General formula (III)

[0038]

[Chemical 10]

(In the formula, R _a and R _b may be the same or different and each represents an alkyl group or an alkenyl group. R _a and R _b may be bonded to each other to form a 4- to 8-membered ring. .)

The secondary amine compound represented by the general formula (III) will be described in more detail. R _a and R _b may be the same or different and each is an alkyl group (eg, methyl,
Represents an ethyl, n-propyl, i-propyl, t-butyl, cyclopropyl) or alkenyl group (eg allyl). These groups may be further substituted with groups other than acidic groups such as carboxyl group, sulfo group and phosphono group. Examples of such groups include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, halogen atoms,
Cyano group, acyl group, nitro group, sulfonyl group, sulfinyl group, acyloxy group, alkoxycarbonyl group,
Carbamoyl group, sulfamoyl group, alkylamino group, dialkylamino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, urethane group, alkoxy group, alkylthio group, aryloxy group, arylthio group, hetero Examples thereof include a ring oxy group, a heterocyclic thio group, a silyl group and a hydroxyl group.

R _a and R _b may combine with each other to form a 4- to 8-membered ring. When R _a and R _b are bonded to each other to form a 4- to 8-membered ring, an alkyl group of R _a and R _b ,
The alkenyl group may be directly bonded or may be bonded via an oxygen atom, a nitrogen atom, a sulfur atom or the like. It is preferable to form a 4- to 8-membered non-aromatic ring. As a typical example, a pyrrolidine ring, a piperidine ring, a morpholine ring, a piperazine ring, a pyrroline ring, an imidazoline ring, an imidazolidine ring, a 1,4-oxazine ring, a 1,4-thiazine ring,
An azetidine ring etc. are mentioned. These rings are also the above R _a
The above groups may be substituted with the substituents listed as the groups which may be substituted.

Specific examples of the compound represented by the general formula (III) and pKa thereof are shown below, but the invention is not limited thereto.

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

These compounds are commercially available and can be easily obtained. The preferred addition amount of the compound represented by the general formula (I) of the present invention or the precursor thereof is Treatment Liquid 1
1.0 × 10 ^{−4 to} 0.5 mol per liter is preferable, 0.001 to 0.1 mol is more preferable, and 0.001 to 0.05 mol is more preferable.

The secondary amine compound of the present invention has the general formula (I)
It is preferably added in a molar ratio of 0.01 to 10 with respect to the compound represented by or the precursor thereof, more preferably 0.05 to 5, and more preferably 0.1 to 1.
In the present invention, containing a compound represented by the general formula (I) or its precursor and a secondary amine compound means that the compound represented by the general formula (I) or its precursor and a secondary amine compound is contained in a stabilizing solution or a preparation liquid. In addition to the presence of, both of them may react to each other and be present as an equilibrium compound.

Although each compound of the present invention is added to the stabilizing solution or the adjusting solution, it may be added to the replenishing solution thereof, which is a preferred embodiment of the present invention. The replenisher used in the present invention is a replenisher that is replenished to maintain the composition of the treatment solution during continuous processing. Each of the replenishers of the present invention controls the concentration of the compound eluted from the light-sensitive material by the processing, and replenishment of the compound to the processing solution, which decreases due to deterioration of the light-sensitive material during processing or deterioration in the automatic processor. By doing so, the performance is adjusted to be constant. Therefore, the decreasing compound has a higher concentration than the processing solution,
In addition, the latter compound has a low concentration. In addition, a compound that is unlikely to change its concentration due to treatment or aging is usually contained at almost the same concentration as the treatment liquid.

As a replenisher, a concentrated replenisher is used from the viewpoint of handleability, and when used, a method of diluting to a required concentration and using as a replenisher is useful. At this time, the higher the concentration rate, the more compact and easy the handling becomes. 1 than the same concentration as the solution used
The concentration is preferably 0 times or more, more preferably 25 times or more.

The stabilizing solution and adjusting solution containing the respective compounds of the present invention will be described. The stabilizing solution is a stabilizing solution used in the final processing step of a color negative film or a color reversal film, or a stabilizing solution used in the stabilizing step in the pre-bath when the final step is a washing step or a rinse step. .. The adjusting solution is a processing solution which is performed between the color developing step and the bleaching step of the color reversal film and is sometimes called a bleaching accelerating bath. In the present invention, the light-sensitive material may be processed with either the stabilizing solution or the adjusting solution, or both may be used.

It is preferable that the stabilizing solution contains various surfactants in order to prevent unevenness of water droplets when the processed light-sensitive material is dried. These surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzene sulfonate type anionic surfactants, higher alcohol sulfate ester salt type anionic surfactants. Agents, alkylnaphthalene sulfonate type anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants However, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. The alkylphenol is particularly preferably octyl, nonyl, dodecyl or dinonylphenol, and the addition mole number of ethylene oxide is particularly preferably 8 to 14. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Further, the stabilizing solution preferably contains various antibacterial agents and fungicides in order to prevent water stains and molds on the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents are JP-A-57 / 1982.
No. 157244 and No. 58-105145, thiazolylbenzimidazole compounds, isothiazolone compounds as shown in JP-A-57-8542, and chlorophenol compounds represented by trichlorophenol. , Bromophenol compounds, organic tin and organic zinc compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole compounds, alkylguanidine compounds, and quaternary compounds such as benzalkonium chloride. Ammonium salts, antibiotics such as penicillin,
Sulfanilamide derivatives known as sulfa drugs, such as Journal Antibacterial and Antifungus Agent (J. Antibact. Antifung.
Agents) Vol.1, No.5, p.207-223 (198)
Examples of the general-purpose antifungal agent described in 3) are 2
You may use together 1 or more types. Also, JP-A-48-83820
Various bactericides described in the above publication can also be used. Specific examples of preferable ones include orthophenylphenol and 2-
(4-thiazolyl) benzimidazole, sodium-2
-Pyridinethiol-1-oxide, 1,2-benzisothiazolin-3-one, sulfanilamide, poly-hexamethylene-biguanidine hydrochloride and the like.

It is also preferable that the stabilizing solution contains various chelating agents. Preferred chelating agents include ethylenediamine quaternary acid, aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, diethylenetriamine-N, N, N ', N'-tetracarboxylic acid. Examples thereof include organic phosphonic acids such as methylenephosphonic acid, and hydrolysates of maleic anhydride polymers described in European Patent 345172A1.

In addition to the compound represented by the general formula (I) of the present invention, a compound which stabilizes a dye image, for example,
Hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, dimethylol urea, organic acids and pH buffering agents may be used in combination. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, alkanolamines described in US Pat. It is also preferable to include a preservative that can be contained in the bleach-fixing solution. As the stabilizing solution, the pH is usually used in the range of 4 to 9, but 6 to 9 is preferable. The replenishing amount of the stabilizing solution is preferably 200 to 1500 ml / m ^{2 of the} light-sensitive material to be processed, particularly 30
0 to 600 ml is more preferable. The processing temperature of the stabilizing solution is preferably 30 to 45 ° C. The processing time is 10 seconds to 2
Minutes are preferable, and 15 to 30 seconds are particularly preferable.

As the adjusting bath, in addition to the respective compounds of the present invention, aminopolycarboxylic acid chelating agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid and cyclohexanediaminetetraacetic acid; sulfurous acid. Sodium, a sulfite such as ammonium sulfite, and various bleaching accelerators described in the bleaching solution such as thioglycerin, aminoethanethiol and sulfoethanethiol may be contained. For the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure, Vol. 191, 19104 (1).
It is preferable to contain the polyoxyethylene compound described in 980). These compounds are
It can be used in the range of 0.1 g to 20 g per liter, but is preferably in the range of 1 g to 5 g. The pH of the adjusting bath is usually in the range of 3 to 11, and preferably 4 to 9, more preferably 4.5 to 7. The treatment time in the conditioning bath is preferably 30 seconds to 5 minutes. The replenishing amount of the adjusting bath is 30 per 1 m ² of the light-sensitive material.
ml to 3000 ml is preferred, but especially 50 ml to 1500 ml
Is preferred. The treatment temperature of the conditioning bath is 20 ° C to 5
0 ° C. is preferable, but 30 ° C. to 40 ° C. is particularly preferable.

The present invention is characterized in that a silver halide color photographic light-sensitive material is processed with the stabilizing solution or the adjusting solution of the present invention to stabilize a dye image without using formalin. ing. Therefore, other than these processing solutions, all processing steps and processing solutions and silver halide color photographic light-sensitive materials can be used. Regarding them, JP-A-2-139544 and 2-8.
54, No. 3-213853 and the like.

[0058]

The present invention will be described below with reference to examples.
The present invention is not limited to these.

Example 1 Fuji Color 160 Professional S was imagewise exposed as a color negative film, and the following processing was carried out using a cine type automatic developing machine as described below. The processed film was subjected to a processing stain test and image stability. I did a test.
The treatment process and the treatment liquid composition are shown below.

Processing step Processing time Processing temperature Replenishment amount * Tank capacity (° C) (ml) (liter) Color development 3 minutes 15 seconds 38.0 600 17 Bleach 45 seconds 38.0 140 5 Fixing (1) 45 seconds 38.0-5 Fixing (2) 45 seconds 38.0 700 5 Stable (1) 20 seconds 38.0-3 Stable (2) 20 seconds 38.0-3 Stable (3) 20 seconds 38.0 400 3 Dry Drying 60 seconds 55 * Replenishment amount per 1 m ² of light-sensitive material Fixing solution is countercurrent method from (2) to (1), and stabilizing solution is also
It is a countercurrent system from (3) to (2) and (2) to (1).
The amount of developer brought into the bleaching process, the amount of bleach brought into the fixing process, the amount of fixer (1) brought into the fixing process (2), and the amount of fixer (2) brought into the stable process. 65 ml, 50 ml, 50 ml, 50 per 1 m ² of light-sensitive material
It was ml. Also, the crossover time is 5
Seconds, and this time is included in the processing time of the previous step.
A ceramic warm air heater was used in the drying step, and the supplied air volume was 8 m ^{3 /} min. Further, the drying air is supplied from below the film drying zone, and the drying temperature is a value measured at the upper part of the drying zone, that is, the uppermost part where the film passes. The composition of the treatment liquid is shown below.

(Color Developer) Unit (g) Mother Liquor Replenisher Diethylenetriaminepentaacetic acid 2.0 2.2 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 5. 2 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β -Hydroxyethyl) amino] aniline sulfate 4.5 6.1 Add water 1000 ml 1000 ml pH (adjusted with KOH and sulfuric acid) 10.05 10.15

(Bleaching solution) Unit (g) Mother liquor Replenishing solution 1,3-Diaminopropane tetraacetic acid Ammonium ferric ammonium monohydrate 144 206 Ammonium bromide 84 120 Ammonium nitrate 17.5 25 Acetic acid 50 71 Water was added. 1000 ml 1000 ml pH [adjusted with ammonia water] 3.5 3.5

(Fixer) Unit (g) Mother liquor Replenisher Ammonium sulfite 19 20.3 Ammonium thiosulfate aqueous solution (700 g / l) 350 ml 375 ml Imidazole 5 5.4 Ethylenediaminetetraacetic acid 15 16 Water was added 1000 ml 1000 ml pH [ammonia Adjusted with water and acetic acid] 7.4 8.1

(Stabilizer) Common unit for mother liquor and replenisher (g) Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 Image stabilizer (Table A) 0.01 mol Amine compound (shown in Table A) 0.01 mol Water added 1.0 liter pH (adjusted with ammonia water) 7.2

[Evaluation of Image Preservability] Each of the samples after the above-mentioned processing was used as a photographic densitometer FSD10 manufactured by Fuji Photo Film Co., Ltd.
After measuring the magenta density at 3
% Was allowed to stand for 2 months, and the concentration was measured again in the same manner. The evaluation was made based on the amount of decrease in magenta density over time. (M fading) The magenta density of each sample after the treatment was 1.5.

[Evaluation of Treatment Contamination] Each sample after the above treatment was visually observed to evaluate contamination. The evaluation criteria are as follows. Rank 1. No dirt is observed 2. Slight stains are observed (1/10 or less of the sample surface, and stains are also slightly cloudy). Clouding is observed (1/10 or more of the sample surface) 4. 4. Adherence is recognized (1/10 or less of the sample surface) 5. Adherence is recognized (more than 1/10 of the sample surface)

[Measurement of Formaldehyde Vapor Pressure] Each stabilizing solution was prepared according to the following formulation, and 100 ml of each was placed in a Petri dish (opening area 80 cm ² ) and placed in a glass closed container having a volume of 5 liters. After aging at 20 ° C. for 7 days, the formaldehyde vapor pressure in the glass container was measured with a formaldehyde L-type direct-reading gas detector tube manufactured by Gastec. (HCHO Concentration) Table A shows each image stabilizer used and the evaluation results.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Chemical 15]

[0071]

[Chemical 16]

[0072]

[Chemical 17]

As can be seen from Table A, No. 2, 10-12
Formaldehyde was detected in, but not others. Compared with the compound represented by the general formula (I) of the present invention or its precursor or a known similar compound alone, the combination of the present invention is remarkably excellent in image storability and does not generate stains on the processed sample. The degree of the effect of improving the image storability cannot be obtained with a primary amine compound or a tertiary amine compound.

Next, the pH of the stabilizing solutions of Nos. 21 to 28 above
Was adjusted to 8.0 and 8.5 with aqueous ammonia, and the same evaluation as to image storability was carried out.
At 0.02 to 0.03, and at pH 8.5 from 0.0 to 0.03.
It was found that the effect of improving image storability was further improved as the pH was increased.

Example 2 As a color reversal film, Fuji Chrome 100 Professional D was imagewise exposed and processed using a cine type automatic processor according to the processing steps shown below. Treatment process time Temperature Replenishment amount * Tank capacity (min) (° C) (liter) (liter) Black and white development 6 38 1.5 12 First washing with water 1 38 7.5 4 Inversion 1 38 1.1 4 Color development 4 38 2.0 12 Adjusting 2 38 1.1 4 Bleaching 4 38 1.3 12 Settling 3 38 1.3 12 Second washing (1) 1 38-4 Second washing (2) 1 38 7.5 4 Stability 1 38 1.1 4 Drying 250 * Replenishment amount per 1 m ² of light-sensitive material The overflow solution of the second washing (2) was introduced into the second washing (1) bath.

The composition of each processing solution was as follows. (Black-and-white developer) Unit (g) Start solution Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 2.0 Diethylenetriamine pentaacetic acid 5 sodium salt 3.0 3.0 Potassium sulfite 30 30 Hydroquinone potassium monosulfonate 20 20 Potassium carbonate 33 33 33 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 2.0 Potassium bromide 2.5 0.9 Potassium thiocyanate 1. 2 1.2 Potassium iodide 2.0 mg 2.0 mg Water was added to 1.0 liter 1.0 liter pH (25 ° C.) 9.60 9.70 The pH was adjusted with hydrochloric acid or potassium hydroxide.

(Reversal Solution) Start Solution / Replenisher Common Unit (g) Nitrilo-N, N, N-trimethylenephosphonic acid, 5 sodium salt 2.0, stannous chloride, dihydrate, 1.0 p-amino acid Phenol 0.1 Sodium hydroxide 8.0 Glacial acetic acid 15 ml Water was added to 1.0 liter Ammonium sulfite 20 Water was added to 1.0 liter pH (25 ° C.) 6.60 pH was adjusted with acetic acid or aqueous ammonia.

(Color Developer) Unit (g) Start Solution Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 2.0 Diethylenetriamine pentaacetic acid 5 sodium salt 2.0 2.0 Sodium sulfite 7.0 7.0 Tripotassium phosphate dodecahydrate 36 36 Potassium bromide 1.0-Potassium iodide 90 mg-Sodium hydroxide 3.0 3.0 Citrazinate 1.5 1.5 1.5 N-ethyl -(Β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.5 10.5 3,6-dithiaoctane-1,8-diol 3.5 3.5 Water was added to 1.0 L 1.0 L pH (25 ° C.) 11.90 12.05 The pH was adjusted with hydrochloric acid or potassium hydroxide.

(Preparation Solution) Common for Start Solution / Replenishment Solution Unit (g) Ethylenediaminetetraacetic acid / disodium salt / dihydrate 8.0 Sodium sulfite 12 2-mercapto-1,3,4-triazole 0.5 pH ( 25 ° C.) 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

(Bleaching Solution) Start Solution / Replenishing Solution Common Unit (g) 1,3-Diaminopropanetetraacetic Acid 3 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Dihydrate 120 Glycolic Acid 40 Acetic Acid 30 Bromide Ammonium 120 Ammonium nitrate 25 Water was added to 1.0 liter pH (25 ° C.) 4.20 pH was adjusted with acetic acid or aqueous ammonia.

(Fixing Solution) Common to Start Solution / Replenishing Solution Unit (g) Ethylenediaminetetraacetic acid / sodium dihydrate / 1.7 Sodium benzaldehyde-o-sulfonate 20 Sodium bisulfite 15 Ammonium thiosulfate (700 g / liter) 250 ml Water was added to 1.0 liter pH (25 ° C.) 6.00 pH was adjusted with hydrochloric acid or aqueous ammonia.

(Stabilizing Solution) Each stabilizing solution of Example 1 was used (common to starting solution / replenishing solution).

The evaluation of the image storability was carried out by using the spots where the magenta density was 0.5 in the gray color-developed portion of the sample subjected to each treatment. The results are similar to those of Example 1, and good results were obtained using the stabilizing solution of the combination of the present invention. In addition, in the above processing, the stabilizer does not contain an image stabilizer (N
The image storability was evaluated in the same manner as above using the solution prepared by adding 0.03 mol / l of each of the image stabilizer and the secondary amine compound shown in Table B to the prepared solution by using o. It was The results are shown in Table B.

[0084]

[Table 3]

As can be seen from Table B, even when the combination bath of the present invention is used, it has a sufficient effect of preventing fading of the magenta dye. When the surface of each sample in Table B was observed, no stain was found.

Example 3 As a photosensitive material, a sample 201 of Example 2 of JP-A-2-90151, a photosensitive material 1 of Example 1 of JP-A-2-93641 and a photosensitive material 9 of Example 3 were used. Process No. 1 of No. 22
Further, when the processing was carried out according to the processing No. 28 of Example 1, the fastness of the dye image was excellent and the light-sensitive material was not stained.

[0087]

By implementing the present invention, the working environment against formaldehyde vapor pressure is improved, the fading prevention effect of dye images is excellent, and the light-sensitive material is not stained.

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[Procedure amendment]

[Submission date] November 30, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

An acyl group, an ester group, a carbamoyl group,
The heterocyclic group and the aryl group may have a substituent,
Examples of these substituents include an alkyl group (eg, methyl, ethyl, n-propyl, butyl, cyclopropyl, hydroxyethyl, methoxymethyl), an alkenyl group (eg, allyl), an aryl group (eg, phenyl, 4 -Tert-butylphenyl), heterocyclic group (for example, 5-pyrazole, 4-pyrazole), halogen atom (for example, chlorine, bromine, fluorine), nitro group, cyano group, sulfo group, carboxyl group, phosphono group, acyl A group (eg, acetyl, benzoyl, propanoyl),
Sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl group (eg, methanesulfinyl), acyloxy (eg, acetoxy), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), carbamoyl group ( For example, carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (eg, sulfamoyl, N-ethylsulfamoyl),
Amino group, alkylamino group (eg, methylamino,
Dimethylamino), acylamino groups (eg acetylamide, benzoylamide), sulfonamide groups (eg methanesulfonamide), imide groups (eg succinimide), ureido groups (eg methylureido), sulfamoylamino groups ( For example, N-methylsulfamoylamino), urethane group (eg, methoxycarbonylamino), alkoxy group (eg, methoxy, ethoxy), alkylthio group (eg, methylthio, octylthio), aryloxy group (eg, phenoxy), An arylthio group (eg, phenylthio),
Examples thereof include a heterocyclic thio group (for example, benzothiazolylthio), a heterocyclic oxy group (1-phenyltetrazole-5-oxy), a formyl group, a hydroxy group or a mercapto group.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

On the other hand, the more preferable precursor is a compound represented by the general formula (II-a) wherein X is-.
O-, R ₁ is H, Y is -SO ₂ - and and R ₂ is -O ^- or compound is -OM, i.e., is a bisulfite adduct of formula (I-a) compounds represented by .. Further, the aldehyde itself represented by the general formula (I) is more preferable than the precursor.

Claims (3)

[Claims] 1. A silver halide color photograph characterized by being treated with a stabilizing solution or adjusting solution containing at least one compound represented by the following general formula (I) or a precursor thereof and at least one secondary amine compound. Method of processing photosensitive material. General formula (I): (In the formula, R is a formyl group, an acyl group, a carboxyl group,
It represents an ester group, a carbamoyl group, a heterocyclic group or an aryl group. ) 2. A stable silver halide color photographic light-sensitive material comprising at least one compound represented by the general formula (I) or its precursor and at least one secondary amine compound according to claim 1. liquid. 3. A silver halide color photographic light-sensitive material preparation containing at least one compound represented by formula (I) according to claim 1 or a precursor thereof and at least one secondary amine compound. liquid.